US1588052A - Basic dyestuffs of the malachite-green series - Google Patents

Description

Patented June 8, 1926.

I 1,588,052 UNITED STATES PATENT OFFICE.

.RUDQLF REYHER, 0]! OFFENBACH-ON-THE-MAIN, GERMANY, ASSIlIGNOR '10 CHEHIBCHE FABRIK GRIESHEIM-ELEKTRON, OF FRANKFORT-dN-THE-MAIN, GERMANY A COB.- PORATION- BASIC nms'rurrs or run iranacnrrnennnn same.

.Io Drawing. Application filed September 2, 1925, Serial No. 54,136, and in Germany September 27, 1984. Y

My invention relates to new basic dyestuffs of the malachite green series, corres ondlng 1n the state of the free bases probab y to the general formula:

oxidation dyestuffs are formed corresponding probably to the general formula:

Alliyl on Aim E N l R1 I R: v N Ri N Ba 01 wherein M represents again a monovalent atom, the condensation can be executed also with dialkylarylamins, whereby after the in which formula RI and R2 represent mon0 subsequent oxldatlon dyestuffs are formed valent radicles' such as hydrogen and alkyl probably to the general groups at least one of these radicles being an mula alkyl group, M a'monovalent atom, whereas Am] I 0H the nuclei I and II may contain further sub- V (L Mm stituents. Q3) I Among the monovalent atoms, which are Y represented by. M in the nucleus III hydrogen and chlorine may be especially men- I tioned- 4 c1 The new dyestuffs may be obtained by condensing one molecular pro ortion of a deriv- 01/ 01 ative of benzaldehyde having the formula: 0H0

wherein M represents again a monovalent cl atom. If M is chlorine, dyestuffs of the following general formula are formed:

Alky on m1 M An i lO nm wherein M represents again a monovalent atom, with two molecular proportions of arylamins, which have monovalent radicles' 01 on the N-atom, at least one of these radicles 1 being an alkyl group, and may contain fur- 0| ther substituents in the nucleus, and by oxi- 01 dizing the leuco bases, thus obtained, which 1 dyestuffs are when dry'bluish to green powders, soluble in water to a blue to green solution, and which dye mordanted cotton, silk and unmordanted artificial silk in beautiful and pure blue, bluish green to green shades.

The condensation ofsuch derivatives of benzaldehyde can be executed for example with two molecular proportions of monoalkylamins, whereby after the subsequent Dyestufis of the present type, but not containing so many chlorine atoms in the positions, stated in the aforesaid formulas, were already known; the present new dyestufis are distinguished by a great capacity of equalizing, by a surprisingly great affinity to artificial silk and by the pure tone of dyeings, obtained therewith.

The derivatives of benzaldehyde of the aforesaid formula were not known hitherto. The 2.3.5-trichlorobenzaldehyde e. g. melting at 76 is obtained in the ordinary way, starting from 2.3.5-trichlorotoluene, the 2.3.4.5-tetrachlorobenzaldehyde, melting at 106106.5, may be obtained by introducing a mixture of chlorine and air into a solution of 4-chloroacetyl-ortho-toluidin in a solvent, resistant to chlorine, by saponifying the 34.5-trichloroacetyl-ortho-toluidin, formed in the main, by substituting the'NH group, being in the 2-position, by chlorine according to the process of Sandmeyer, by chlorinating the 2.3.4.5-tetrachlorotoluene, thus formed, in. the side chain and by saponifying the 2.3.4.5-tetrachlorobenzalchloride, thus formed. The 2.3.4.5-tetrach1orobenzaldehyde may also be obtained, starting from a mixture together with the 2.3.5.6-tetrachlorobenzaldehyde by separatin the isomers according to the diflerent so ubility of their bisulfite-compounds. Such mixtures of the isomers tetrachlorobenzaldehydes can be obtained in the same way, as above mentioned for preparing pure 2.3.4.5-tetrachlorobenzaldehyde, starting from mixtures of 2.3.4.5 and 2.3.5.6-tetrachlorotoluene, which are obtained by saponifying mixtures of 3.4.5.- and 3.5.6-trichloroacidyl-ortho-toluidin and by substituting the NH,- group, being in 2- position of both isomers, by chlorine according to the process of, Sandmeyer. The mixtures of 3.4.5- and 3.5.6-trichloroacidyl-ortho-toluidin can be prepared starting from an acidyl-ortho-toluidin by introducing a mixture of chlorine and air in its solution .in a solvent, resistant to chlorine, or in the same manner starting from a mixture of the acidyl-compounds of 4- and 6- chloro-ortho-toluidin as obtainable by chlorinating orth-o-nitro-toluene according to the known process, by reducing and acidulating in a very cheap manner.

The following examples illustrate the nature of the invention, the parts being by weight.

Ewample 1.

10.5 parts of melting at 7576 and 14.8 parts of monoethyl-ortho-toluidin, are stirred with 9 parts of sulfuric acid of 47 B. at 105110 for 30 hours. After oversaturatingwith asolution of carbonate of soda the excess of the base is expelled by steam, the leuco base,

being solid when cold, is filtered and dried.

The leuco base, thus obtained, is dissolved in 200 parts of water with 17 arts of hydrochloric acid of 22 B. and 3 parts of glacial acetic acid and the cold solution is oxidized by adding 31 parts of a paste, containing 49.4 p. c. of superoxide of lead. while stirring. After half an hour the lead is precipitated by 7.8 parts of sulfate of 'of lead is filtered off and the is salted out with common sa t. The dye- 2.3.5.-trichlorobenzaldehyde,

soda. -After heating to 70 C. and adding such a quantity of hot water, that all the is filtered and dried. It is' soluble in waterto a beautifulblue solution and d esmordanted cotton, also silk and arti cial' silk l in pure blue shades.

Example 2.

12.2 parts of 2.3.4.5-tetrachlorobenzaldehyde, melting at 106106.5 and 16.4 parts of diethylanilin are stirred with 9 parts of sulfuric acid of 47- B.--at 110115 for 40 hours. After oversaturating with a solution of carbonate of soda the excess of .diethylanilin f is expelled with steam. For oxidation the obtained 24.3 parts of the leuco base are dissolved in 200 parts of water with 17 parts of hydrochloric acid of 22 B. and to 3 parts of lacialacetic acid and to the cold solution %add, while stirring, 22 parts of a paste, containing 57 p. 0; sn eroxide of lead. After about hour the sad is precipitated with 7.8 parts of'sulfateof soda. after moderately heating ,the sulfate een solution stuff separated is resinous, while hot, crystalline'and greenish'opalescent, while cold. The dyestufl, having' robably. in the state of the free base'tlie ormula:

O] i 01 a is filtered off and dried. Mordanted cotton, silk and artificial silk are dyed in very pure and even bluish green tones such as not hitherto obtainable with anyone of the known unmixed dyestufis.

In the same manneralso dimethylaniliu bluish green to green general formula:

and other arylamins and other derivatives of benzaldehyde of this kind may be used for condensation.

The dyestufls may ducing color lakes.

Now what I claim is: 1. As new compounds basic dyestuffs of the malachite green series, corresponding probably in the state of the free bases to the be used also for proin which formula R and R, represent monovalent radicles, at least one of these radicles being an alkyl group, M a monovalent atom, which dyestufis may densing one molecular roportion of a derivative of benzaldehyde of the formula:

Al! I OH Y Alkyl N Alkyl Alkyl in which formula M'represents a monovalent be obtained by conatom which may be obtained by condensing: one molecular proportion of a derivative of benzaldehyde of the formula:

CHO

' wherein M represents again a monovalent atom, with two molecular proportions of dialkylanilins and by oxidizing the leuco bases, thus obtained, which dyestufl's are when dry, bluish to green powders, soluble in Water to a blue to green solution, and dye mordanted cotton, silk and unmordanted artificial silk in beautiful and pure blue, bluish green to green shades.

3. As new compounds basic dyestufls of the malachite green series, corresponding probably in the state of the free bases to the general formula:

Alkyl on Alkyl K which may be obtained by condensing one molecular proportion of 2.3.4.5-tetrachlorobenzaldehyde with two molecular propor-' tions of dialkylanilins and by oxidizing the leuco bases, thus obtained, which dyestufis are when dry bluish to green powders, soluble in Water to a blue to green solution, and dye mordanted cotton, silk and unmordanted, artificial silk in beautiful .and pure blue, bluish green to green shades. I

4. As a new compound a basic dyestufi of the malachite green series, correspond ng robably in the state of the free base to the ormula which maybe obtained by condensing: one ton, silk and' unmordanted artificial silk in molemilar 1'nop(,n'tion of 2.3.4.5-tetrachlorobeautiful and pure bluish green shades. benzuldehycle with two molecular propor- In testimony, that I claim the foregoing tions of rliethylanilin and by oxidizing the as my invention, I have signed my name,

5 lcuco base, thus obtained, which dyestufi is this 22d clay of August, 1-925.

when dry a green powder, soluble in water 1 to a green solution, and dyes mordanted cot- Du. RUDOLF REYHER.